CN103178239A - Positive electrode for secondary battery and manufacturing method of positive electrode for secondary battery - Google Patents
Positive electrode for secondary battery and manufacturing method of positive electrode for secondary battery Download PDFInfo
- Publication number
- CN103178239A CN103178239A CN2012105715798A CN201210571579A CN103178239A CN 103178239 A CN103178239 A CN 103178239A CN 2012105715798 A CN2012105715798 A CN 2012105715798A CN 201210571579 A CN201210571579 A CN 201210571579A CN 103178239 A CN103178239 A CN 103178239A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- active material
- positive electrode
- secondary cell
- anode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims description 36
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 214
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 179
- 239000007774 positive electrode material Substances 0.000 claims abstract description 97
- 229920000642 polymer Polymers 0.000 claims abstract description 46
- 125000000524 functional group Chemical group 0.000 claims abstract description 35
- 239000002245 particle Substances 0.000 claims abstract description 15
- 229910052744 lithium Inorganic materials 0.000 claims description 95
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 92
- 238000006722 reduction reaction Methods 0.000 claims description 54
- 230000009467 reduction Effects 0.000 claims description 49
- 238000000034 method Methods 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 23
- 239000003792 electrolyte Substances 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 17
- 150000001721 carbon Chemical group 0.000 claims description 16
- 229910052799 carbon Inorganic materials 0.000 claims description 16
- 239000011572 manganese Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 150000004982 aromatic amines Chemical class 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 239000006230 acetylene black Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 5
- 229920001721 polyimide Polymers 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 238000004381 surface treatment Methods 0.000 claims description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000006229 carbon black Substances 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 239000011574 phosphorus Substances 0.000 claims description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 239000004962 Polyamide-imide Substances 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 claims description 3
- 229920002312 polyamide-imide Polymers 0.000 claims description 3
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 abstract 3
- 239000011230 binding agent Substances 0.000 abstract 2
- 239000002482 conductive additive Substances 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 57
- 239000000463 material Substances 0.000 description 34
- 239000000523 sample Substances 0.000 description 27
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- 239000000376 reactant Substances 0.000 description 22
- 229910002804 graphite Inorganic materials 0.000 description 19
- 239000010439 graphite Substances 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 19
- 150000001875 compounds Chemical class 0.000 description 17
- 239000000853 adhesive Substances 0.000 description 16
- 230000001070 adhesive effect Effects 0.000 description 16
- -1 amino, carboxyl Chemical group 0.000 description 16
- 238000007600 charging Methods 0.000 description 15
- 229910052493 LiFePO4 Inorganic materials 0.000 description 14
- 125000004429 atom Chemical group 0.000 description 13
- 239000012752 auxiliary agent Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 125000004430 oxygen atom Chemical group O* 0.000 description 12
- 230000008569 process Effects 0.000 description 11
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000004411 aluminium Substances 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 229910052782 aluminium Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 238000007599 discharging Methods 0.000 description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 8
- 230000005611 electricity Effects 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- 239000004593 Epoxy Substances 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910004283 SiO 4 Inorganic materials 0.000 description 7
- 239000002131 composite material Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 239000006185 dispersion Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000007773 negative electrode material Substances 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- HEZMWWAKWCSUCB-PHDIDXHHSA-N (3R,4R)-3,4-dihydroxycyclohexa-1,5-diene-1-carboxylic acid Chemical compound O[C@@H]1C=CC(C(O)=O)=C[C@H]1O HEZMWWAKWCSUCB-PHDIDXHHSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 5
- 239000002800 charge carrier Substances 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000004743 Polypropylene Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000004683 dihydrates Chemical class 0.000 description 4
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 4
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 4
- 229910001386 lithium phosphate Inorganic materials 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 239000002033 PVDF binder Substances 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 229910000676 Si alloy Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000005030 aluminium foil Substances 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- 238000009413 insulation Methods 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- 150000002697 manganese compounds Chemical class 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 238000001542 size-exclusion chromatography Methods 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910013275 LiMPO Inorganic materials 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- 229910015868 MSiO Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical group [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 241000156302 Porcine hemagglutinating encephalomyelitis virus Species 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 229910014307 bSiO Inorganic materials 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 229910001423 beryllium ion Inorganic materials 0.000 description 2
- PWOSZCQLSAMRQW-UHFFFAOYSA-N beryllium(2+) Chemical compound [Be+2] PWOSZCQLSAMRQW-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000006182 cathode active material Substances 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical group [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000004567 concrete Substances 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010281 constant-current constant-voltage charging Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000000935 solvent evaporation Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 238000004876 x-ray fluorescence Methods 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 101000598921 Homo sapiens Orexin Proteins 0.000 description 1
- 101001123245 Homo sapiens Protoporphyrinogen oxidase Proteins 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910011281 LiCoPO 4 Inorganic materials 0.000 description 1
- 229910010586 LiFeO 2 Inorganic materials 0.000 description 1
- 229910015645 LiMn Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013086 LiNiPO Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 102100029028 Protoporphyrinogen oxidase Human genes 0.000 description 1
- 229910000577 Silicon-germanium Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 238000004378 air conditioning Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000005264 aryl amine group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229910021446 cobalt carbonate Inorganic materials 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- JQVALDCWTQRVQE-UHFFFAOYSA-N dilithium;dioxido(dioxo)chromium Chemical compound [Li+].[Li+].[O-][Cr]([O-])(=O)=O JQVALDCWTQRVQE-UHFFFAOYSA-N 0.000 description 1
- GMKDNCQTOAHUQG-UHFFFAOYSA-L dilithium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=S GMKDNCQTOAHUQG-UHFFFAOYSA-L 0.000 description 1
- BBLSYMNDKUHQAG-UHFFFAOYSA-L dilithium;sulfite Chemical compound [Li+].[Li+].[O-]S([O-])=O BBLSYMNDKUHQAG-UHFFFAOYSA-L 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 150000002642 lithium compounds Chemical class 0.000 description 1
- 229910001947 lithium oxide Inorganic materials 0.000 description 1
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 description 1
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 1
- GLNWILHOFOBOFD-UHFFFAOYSA-N lithium sulfide Chemical compound [Li+].[Li+].[S-2] GLNWILHOFOBOFD-UHFFFAOYSA-N 0.000 description 1
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 235000006748 manganese carbonate Nutrition 0.000 description 1
- 239000011656 manganese carbonate Substances 0.000 description 1
- 229940093474 manganese carbonate Drugs 0.000 description 1
- HDJUVFZHZGPHCQ-UHFFFAOYSA-L manganese(2+);oxalate;dihydrate Chemical compound O.O.[Mn+2].[O-]C(=O)C([O-])=O HDJUVFZHZGPHCQ-UHFFFAOYSA-L 0.000 description 1
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 1
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013464 silicone adhesive Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
- H01M4/622—Binders being polymers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0404—Methods of deposition of the material by coating on electrode collectors
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
Abstract
The positive electrode active material layer includes a plurality of particles of a positive electrode active material and a reaction mixture where reduced graphene oxide is bonded to a polymer having a functional group as a side chain. The reduced graphene oxide has a sheet-like shape and high conductivity and thus functions as a conductive additive by being in contact with the plurality of particles of the positive electrode active material. The reaction mixture serves as an excellent binder since the reduced graphene oxide is bonded to the polymer. Therefore, even a small amount of the reaction mixture where the reduced graphene oxide is covalently bonded to the polymer excellently serves as a conductive additive and a binder.
Description
Technical field
The present invention relates to the manufacture method of a kind of anode of secondary cell and anode of secondary cell.
Background technology
In recent years, the portable equipment such as smart mobile phone and portable game machine is popularized.In addition, because people improve day by day to the care of environmental problem, hybrid vehicle and electric automobile attract attention, and the importance of the secondary cells such as lithium secondary battery is improved.
The basic structure of secondary cell is to make the structure of electrolyte between positive pole and negative pole.The typical structure of positive pole and negative pole is the structure that has collector body and be arranged on the active material on collector body.In lithium secondary battery, use can be with the material of lithium ion occlusion and the release active material as positive pole and negative pole.
For enlarge and electrolyte between contact area, positive active material mostly is greatly the particle shape.The general formation positive electrode active material layer such as mixed adhesive and conductive auxiliary agent and it is arranged on forms positive pole on collector body in particle shape positive active material.
Adhesive has particle shape positive active material is bonded to each other and with positive active material and the bonding function that improves the intensity of positive electrode active material layer of collector body.The typical material of adhesive is Kynoar (PVDF), butadiene-styrene rubber (SBR), carboxymethyl cellulose (CMC) etc.In addition, conductive auxiliary agent has provides the feed lines (supply path) of electronics to reduce the function of the contact resistance between positive active material and collector body to positive active material.Typical material as conductive auxiliary agent is acetylene black.
Yet adhesive and conductive auxiliary agent etc. is not help the cell reaction material of (being equivalent to occlusion and the release of lithium ion when adopting lithium secondary battery).Therefore, the ratio of the adhesive in positive electrode active material layer and conductive auxiliary agent etc. more increases, and the ratio of positive active material more reduces and makes the capacity loss of the unit volume of positive electrode active material layer.
For example, patent documentation 1 discloses as conductive auxiliary agent and has used carbon black and use the lithium secondary battery of the mixture of Kynoar and polyamide-imides as adhesive, and the ratio of the positive active material in anode mixture (positive electrode active material layer) is 87wt% only.
[patent documentation 1] Japanese Patent Application Publication 2004-335188 communique
Summary of the invention
In view of the above problems, one of purpose of a mode of the present invention is the shared ratio of raising positive active material in positive electrode active material layer and the intensity that improves positive electrode active material layer.In addition, one of purpose of the present invention is to improve the capacity of the unit volume of secondary cell.
In order to achieve the above object, a mode of the present invention is as the conductive auxiliary agent reactant that adhesive uses the graphene oxide that is reduced to be combined with the polymer with functional group of holding concurrently.Particularly, mixed cathode active material, graphene oxide and side chain have the polymer of functional group in conjunction with graphene oxide and polymer.Then, graphene oxide was also formed originally reactant that the graphene oxide be reduced is combined with polymer and used as the conductive auxiliary agent adhesive of holding concurrently.
In this manual, Graphene refers to have lyriform pore that the ion that makes lithium etc. passes through and by a plate sheet of the carbon molecular composition of an atomic layer with π key, perhaps is laminated with the laminated body of 2 to 100 these thin slices.In addition, this laminated body can be called multi-layer graphene.
In addition, in this manual, graphene oxide refers to oxidized Graphene.In other words, graphene oxide is a kind of material, and wherein oxygen atom is combined with the carbon atom that Graphene has.More particularly, epoxy radicals, carbonyl, carboxyl or hydroxyl etc. are combined with the polynary nuclear carbon atoms such as hexatomic ring that Graphene has.In addition, for graphene oxide and the graphene oxide difference that is reduced described later are come, in this manual, will be in the summation of C=C key, C-C key, c h bond, C-O key, C=O key, O=C-O key the shared ratio of C=C key be called graphene oxide lower than 5% Graphene.In addition, in this manual graphene oxide refers to that in the summation of carbon atom, oxygen atom, the nitrogen-atoms shared ratio of oxygen atom surpasses the Graphene of 15 atom %.
In this manual, the graphene oxide that the graphene oxide that is reduced has referred to reduce.Therefore, the graphene oxide that is reduced can be called and be formed with π key between carbon atom by reduction and (namely result from the sp of C=C key
2Track) graphene oxide.Thus, also the graphene oxide that is reduced can be called in the summation of C=C key, C-C key, c h bond, C-O key, C=O key, the O=C-O key shared ratio of C=C key is graphene oxide more than 5%.
In addition, also the graphene oxide that is reduced can be called the graphene oxide that ratio by oxygen reduction has reduced.Therefore, the graphene oxide that is reduced can be called also that the shared ratio of oxygen atom is more than 1 atom % and the graphene oxide below 15 atom % in the summation of carbon atom, oxygen atom, nitrogen-atoms.
In addition, also the graphene oxide that is reduced can be called the graphene oxide that conductivity is improved by the π key between reduction Formed atom.Therefore, also the graphene oxide that is reduced can be called conductance is 10
-6The graphene oxide that S/m is above.
A mode of the present invention is a kind of anode of secondary cell, and this anode of secondary cell comprises: the positive electrode active material layer on collector body, and this positive electrode active material layer comprises: a plurality of particle shape positive active materials; And at least one in the graphene oxide that is reduced and multilayer graphene oxide has with side chain the reactant that the polymer of functional group is combined, wherein, at least a portion of a plurality of particle shape positive active materials contacts with at least a portion of the graphene oxide that is reduced.
In addition, above-mentioned functional group is preferably amino.
In addition, above-mentioned combination is preferably the covalent bond between carbon atom and nitrogen-atoms.
In addition, the sticky end coating preferably is set between collector body and positive electrode active material layer.
In addition, the sticky end coating preferably includes following mixture, and this mixture is more than one the mixture in more than one and acetylene black, carbon black, Graphene, the graphene oxide that is reduced and carbon nano-tube in Kynoar, polyimides, carboxymethyl cellulose and Sodium Polyacrylate.
In addition, another mode of the present invention is a kind of manufacture method of anode of secondary cell, and the method comprises the steps: to mix a plurality of particle shape positive active materials, graphene oxide and water; Mixture interpolation aqueous solutions of polymers to a plurality of particle shape positive active materials, graphene oxide and water is made slurry; Slurry is coated on collector body; Slurry is carried out drying form positive electrode active material layer; And the graphene oxide that positive electrode active material layer has is reduced.
In addition, preferably soak collector body and to the electrolyte of electrode in the current potential of collector body supply graphene oxide generation reduction reaction is carried out the reduction of the graphene oxide that positive electrode active material layer has.
In addition, preferably before being coated in slurry on collector body, collector body is carried out surface treatment.
According to a mode of the present invention, can improve the ratio of the positive active material in positive electrode active material layer and improve the intensity of positive electrode active material layer.In addition, can improve the capacity of the unit volume of secondary cell.
Description of drawings
Figure 1A and Figure 1B are sectional view and the vertical views of the positive pole of a mode of the present invention;
Fig. 2 is the figure of example that the combination of graphene oxide in the positive pole of a mode of the present invention and polymer is shown;
Fig. 3 A and Fig. 3 B are the figure of explanation Coin shape lithium secondary battery;
Fig. 4 A and Fig. 4 B are the figure of explanation cylindrical lithium secondary battery;
Fig. 5 is the figure of explanation electronic equipment;
Fig. 6 A to Fig. 6 C is the figure of explanation electronic equipment;
Fig. 7 A and Fig. 7 B are the figure of explanation electronic equipment;
Fig. 8 A and Fig. 8 B are the figure that the charge-discharge characteristic of embodiment 1 is shown;
Fig. 9 A and Fig. 9 B are the figure that the charge-discharge characteristic of comparative example 1 is shown;
Figure 10 is the figure of the charge-discharge characteristic of comparing embodiment 1 and comparative example 1;
Figure 11 is the figure that the charge-discharge characteristic of embodiment 2 is shown;
Figure 12 is the figure of measurement result that the FT-IR of embodiment 3 is shown;
Figure 13 is the figure of measurement result that the FT-IR of embodiment 3 is shown;
Figure 14 is the figure of measurement result that the XPS of embodiment 4 is shown;
Figure 15 is the figure of measurement result that the XPS of embodiment 4 is shown.
Embodiment
Below, illustrate referring to the drawings execution mode.But, execution mode can be implemented with a plurality of different modes, the person of an ordinary skill in the technical field can understand a fact at an easy rate, is exactly that its mode and detailed content can be transformed to various forms and not break away from aim of the present invention and scope thereof.Therefore, the present invention should not be interpreted as only being limited in the content that execution mode shown below puts down in writing.
Note, for easy understanding content, the position of shown each structure such as accompanying drawing, size and scope etc. do not represent actual position, size and scope etc. sometimes.Therefore, disclosed invention not necessarily is confined to disclosed position, size, the scopes etc. such as accompanying drawing.
In the present embodiment, with reference to Figure 1A, Figure 1B and Fig. 2, an example of the positive electrode for lithium secondary battery of a relevant mode of the present invention is described.
＜anodal structure 〉
Figure 1A and Figure 1B are respectively sectional view and the vertical views of an example of positive pole 301.In anodal 301, be provided with positive electrode active material layer 201 on collector body 101.Positive electrode active material layer 201 has positive active material 102 and the graphene oxide that is reduced and side chain have the reactant 103 that the polymer of functional group is combined.
＜adhesive 〉
In anodal 301, reactant 103 is as adhesive.The polymer that the graphene oxide that is reduced in reactant 103 and side chain have functional group is preferably by covalent bonds, because the adhesion of covalent bond is very strong.In addition, in this specification etc., polymer refers to the compound that a plurality of monomer polymerizations form, to its molecular weight and not restriction of the degree of polymerization.As polymer, can use the degree of polymerization is the oligomer of 2 to 100 left and right.
Have the functional group in the polymer of functional group as side chain, can use amino, carboxyl, carbonyl, hydroxyl, azo group, diazo, mercapto etc.In addition, have the polymer of functional group as side chain, also can use triazo-compound.
For example, can enumerate many arylamine, polyimides, polyamide-imides etc. as having amino polymer.
When use had amino polymer, the graphene oxide that is reduced and the covalent bond between polymer were C-N key (with reference to Fig. 2).Therefore, during reactant 103 that the polymer that has functional group when the graphene oxide that utilizes Fu Shi conversion infrared spectrum analysis instrument (FT-IR) to measure to be reduced and side chain is combined, might observe the absorption of C-N key.In addition, utilize inductively coupled plasma (ICP:Inductively Coupled Plasma) emission spectrographic analysis, X-ray fluorescence spectra (XRF:X-Ray Fluorescence) analysis etc. might detect nitrogen.In addition, liquid chromatograph mass spectrography (LC/MS) is analyzed, gas chromatography-mass spectrography (GC/MS) analysis etc. might detect contains nitrogen compound.
In addition, no matter use which kind of functional group, utilize SEC (SEC:Size Exclusion Chromatography) might detect its molecular weight ratio by the graphene oxide that is reduced before covalent bonds and the large compound of molecular weight of polymer.
In addition, also can use the conducting polymers such as polymer with Oligopoly thiophene skeleton.When using conducting polymer, can further improve the conductivity of positive electrode active material layer 201, so be preferred.
As the graphene oxide that is reduced, use the graphene oxide of processing through reduction.As the graphene oxide that is reduced, particularly, the shared ratio of oxygen atom is more than 1 atom % and the graphene oxide below 15 atom % in by the summation of the carbon atom of the mensuration such as x-ray photoelectron power spectrum (XPS:X-Ray Photoelectron Spectroscopy), oxygen atom, nitrogen-atoms such as using.Perhaps, use that the shared ratio of C=C key is more than 5% in by the summation of the C=C key of the mensuration such as XPS, C-C key, c h bond, C-O key, C=O key, O=C-O key, be preferably more than 10%, more preferably the graphene oxide more than 30%.Perhaps, using conductance is 10
-6The graphene oxide that S/m is above.
Graphene oxide has the functional groups such as epoxy radicals, carboxyl, carbonyl or hydroxyl due to graphene oxide, so can be combined with the polymer that side chain has functional group by above-mentioned functional group.The reactant of being combined by the polymer that graphene oxide and side chain is had functional group reduces processes to form the reactant that polymer that the graphene oxide that is reduced and side chain have functional group is combined.Form by graphene oxide being reduced process the graphene oxide that is reduced, can improve conductivity.Therefore, a small amount of graphene oxide that is reduced and side chain have reactant 103 that the polymer of functional group is combined also can be as the good conductive auxiliary agent adhesive of holding concurrently.
＜positive active material 〉
As the material of positive active material, can use LiFeO
2, LiCoO
2, LiNiO
2, LiMn
2O
4, V
2O
5, Cr
2O
5, MnO
2Deng compound.
Perhaps, (general formula is LiMPO can to use the lithium-contained composite oxide of olivine-type structure
4(M is Fe(II), Mn(II), Co(II), Ni(II) in more than one).Be LiMPO as general formula
4Exemplary, can enumerate LiFePO
4, LiNiPO
4, LiCoPO
4, LiMnPO
4, LiFe
aNi
bPO
4, LiFe
aCo
bPO
4, LiFe
aMn
bPO
4, LiNi
aCo
bPO
4, LiNi
aMn
bPO
4(a+b is below 1,0＜a＜1,0＜b＜1), LiFe
cNi
dCo
ePO
4, LiFe
cNi
dMn
ePO
4, LiNi
cCo
dMn
ePO
4(c+d+e is below 1,0＜c＜1,0＜d＜1,0＜e＜1), LiFe
fNi
gCo
hMn
iPO
4Lithium compounds such as (f+g+h+i are below 1,0＜f＜1,0＜g＜1,0＜h＜1,0＜i＜1).
Perhaps, can use general formula to be Li
(2-j)MSiO
4(M is Fe(II), Mn(II), Co(II), Ni(II) in more than one, 0≤j≤2) etc. lithium-contained composite oxide.Be Li as general formula
(2-j)MSiO
4Exemplary, can enumerate Li
(2-j)FeSiO
4, Li
(2-j)NiSiO
4, Li
(2-j)CoSiO
4, Li
(2-j)MnSiO
4, Li
(2-j)Fe
aNi
bSiO
4, Li
(2-j)Fe
aCo
bSiO
4, Li
(2-j)Fe
kMn
1SiO
4, Li
(2-j)Ni
kCo
1SiO
4, Li
(2-j)Ni
kMn
lSiO
4(k+l is below 1,0＜k＜1,0＜l＜1), Li
(2-j)Fe
mNi
nCo
qSiO
4, Li
(2-j)Fe
mNi
nMn
qSiO
4, Li
(2-j)Ni
mCo
nMn
qSiO
4(m+n+q is below 1,0＜m＜1,0＜n＜1,0＜q＜1), Li
(2-j)Fe
rNi
sCo
tMn
uSiO
4Lithium compounds such as (r+s+t+u are below 1,0＜r＜1,0＜s＜1,0＜t＜1,0＜u＜1).
In addition, when the charge carrier ion is alkali metal ion, alkaline-earth metal ions, beryllium ion beyond lithium ion or magnesium ion, also (for example can use alkali metal as positive active material, sodium, potassium etc.), alkaline-earth metal (for example, calcium, strontium, barium etc.), beryllium or magnesium replaces the lithium in above-mentioned lithium compound and lithium-contained composite oxide.
Especially preferably use LiFePO
4, because it has following advantage: use the iron that is dirt cheap; Fe is occuring
2+/ Fe
3+Redox material in LiFePO
4It is the material that presents high potential (3.5V left and right); Has good cycle characteristics; Theoretical capacity is 170mAhg
-1The left and right; Level density is high.
＜collector body 〉
As collector body, can use aluminium, stainless steel etc. to have the material of high conductivity.Especially preferably use aluminium, make electrode have chemical stability because aluminium forms passive state.In addition, can suitably select paper tinsel shape, tabular or netted etc. shape.
In the present embodiment, an example of the manufacture method of the positive electrode for lithium secondary battery of a relevant mode of the present invention described.
＜graphene oxide 〉
At first, the manufacture method of graphene oxide described.Graphene oxide can utilize the oxidizing process manufacturing that is called as Modified Hummers method.Modified Hummers method is a kind of method, wherein add the sulfuric acid solution, aquae hydrogenii dioxidi etc. of potassinm permanganate and cause that oxidation reaction manufacturing contains the suspension of graphite oxide in the single crystal graphite powder, and making this graphite oxide rive to form the dispersion liquid that contains graphene oxide.Due to the oxidation of the carbon in graphite, so graphite oxide has the functional groups such as epoxy radicals, carbonyl, carboxyl, hydroxyl.Apply ultrasonic vibration by the suspension that this is contained graphite oxide and the long graphite oxide of interfloor distance is rived and graphene oxide is separated, can make the dispersion liquid that contains graphene oxide simultaneously.
Make the graphene oxide that graphite oxide rives to make also have the functional groups such as epoxy radicals, carbonyl, carboxyl, hydroxyl.Because graphene oxide has above-mentioned functional group, so the interfloor distance between a plurality of Graphene is longer than graphite.In addition, also can suitably adopt the manufacture method of Modifi ed Hummers method graphene oxide in addition.By removing solvent from the dispersion liquid that contains graphene oxide, can obtain graphene oxide.
In having the solution of polarity, graphene oxide is charged owing to having functional group, so graphene oxide is not easy to assemble each other.So graphene oxide easily disperses equably in having the solution of polarity.
The length of one length of side of the graphene oxide that uses in addition, (scale size) is preferably a few μ m to tens μ m.
In addition, can use as graphene oxide the graphene oxide dispersion liquid of selling on the graphene oxide sold on market or market.
＜positive active material 〉
Then, the manufacture method of positive active material described.At first, mix following compound with the composition of appointment and form composite material, this compound is general formula LiMePO
4The lithium-containing compound of the supply source that becomes Li in (note, Me represents manganese (Mn) or iron (Fe)); Become the phosphorus-containing compound of the supply source of P; And become Me supply source iron containing compounds or contain manganese compound.
As lithium-containing compound, for example can use lithium carbonate (Li
2CO
3), lithia (Li
2O), lithium sulfide (Li
2S), lithium peroxide (Li
2O
2), lithium sulfate (Li
2SO
4), lithium sulfite (Li
2SO
3), lithium thiosulfate (Li
2S
2O
3), lithium chromate (Li
2CrO
4) and lithium bichromate (Li
2Cr
2O
7) etc. lithium salts.
As containing manganese compound, such as using manganese oxide, manganese oxalate dihydrate (II) or manganese carbonate (II) etc.In addition, when when containing manganese compound and being applied to composite material, making the electrode material that comprises lithium manganese phosphate with this.In addition, as iron containing compounds, such as using iron oxide, ferric oxalate (II) dihydrate or ferric carbonate (II) etc.In addition, when this iron containing compounds is applied to composite material, can make the electrode material that comprises LiFePO4.
In addition, by general formula LiMePO
4In the lithium phosphate compound of expression, can use cobalt (Co), nickel (Ni) as Me.As cobalt compound or nickel compound containing, can use oxide (cobalt oxide, nickel oxide), oxalates (cobalt oxalate, nickel oxalate) or the carbonate (cobalt carbonate, nickelous carbonate) etc. of cobalt or nickel.
In addition, as phosphorus-containing compound, for example can use ammonium dihydrogen phosphate (NH
4H
2PO
4), phosphorus pentoxide (P
2O
5) etc. phosphate.
As the method for mixing above-mentioned each compound, for example can enumerate ball mill and process.Its concrete grammar below is shown: for example, add the high solvents of volatility such as acetone in each compound after weighing, use the ball (sphere diameter φ is as more than 1mm and below 10mm) of metal or pottery to be rotated number as 50rpm is above and below 500rpm, rotational time is more than 30 minutes and the processing below 5 hours.Process by carrying out ball mill, can carry out the micronize of compound in mixing cpd, and the micronize of material of the electrode after can realizing making.In addition, process by carrying out ball mill, can mix equably the compound as raw material, make and can improve the crystallinity that electrode is afterwards used material.In addition, as solvent, except acetone, also can use the undissolved solvents of its Raw such as ethanol, methyl alcohol.
Then, make the solvent evaporation composite material is heated after, carry out the first heat treatment (preroast).As the first heat treatment, with more than 300 ℃ and the temperature below 400 ℃ carry out more than 1 hour and below 20 hours, be preferably the processing below 10 hours, get final product.Although when the excess Temperature of the first heat treatment (preroast), sometimes the particle diameter of positive active material is excessive and battery behavior is reduced, but by with more than 300 ℃ and the low temperature below 400 ℃ carry out the first heat treatment (preroast), can form nucleus when suppressing crystalline growth.Therefore, can realize the electrode micronize of material.
In addition, the first heat treatment is preferably under nitrogen atmosphere, carry out under the inert gas atmosphere such as rare gas (helium, neon, argon, xenon etc.) or nitrogen.
After carrying out the first heat treatment, burned material is carried out washing procedure.As cleaning solution, can use the cleaning solution of neutrality or alkalescence, for example can use pure water or weak alkaline aqueous solution (for example, the sodium hydrate aqueous solution of about pH9.0 etc.).For example, after at room temperature washing 1 hour, filtering solution and reclaim burned material and get final product.
By the washing burned material, can reduce the impurity that is included in burned material, and can make highly purified lithium phosphate compound.Be lowered and obtain in the lithium phosphate compound of high-purity in impurity concentration, crystallinity also is improved, so can increase the amount of the charge carrier ion that is inserted into and is broken away from when discharging and recharging.
Then, use mortar etc. is pulverized the material that washs, and processes by ball mill same as described above and mixes.Afterwards, make the solvent evaporation the material that mixes is heated after, carry out the second heat treatment (main roasting).
As the second heat treatment, carry out more than 1 hour and the processing below 20 hours (preferably carrying out the processing below 10 hours) with the temperature that (is preferably 600 ℃ of left and right) more than 500 ℃ and below 800 ℃, get final product.In addition, preferably the second heat treatment temperature is set as higher than the first heat treatment temperature.
By above-mentioned operation, can make and to be applied to the lithium phosphate compound that electrode is used material.
＜positive electrode active material layer 〉
Then, the polymer that positive active material, graphene oxide and side chain by above-mentioned operation manufacturing is had a functional group carries out weighing.
The weight ratio that has the polymer of functional group about positive active material, graphene oxide and side chain, preferably be increased in overall weight in the scope of the intensity that can keep sufficient conductivity and electrode in the shared ratio of positive active material.Particularly, more than the ratio of graphene oxide is preferably 1wt% and below 20wt%, more preferably more than 2wt% and below 3wt%.More than being set as 1wt% by the ratio with graphene oxide, can reducing contact resistance between positive active material and the contact resistance between positive active material and collector body and improve conductivity.And, be set as below 20wt% by the ratio with graphene oxide, can make the high positive pole of capacity of the unit volume of positive electrode active material layer.
Then, mixed cathode active material and graphene oxide.In the present embodiment, adopt the wet mixed that adds water and use the rotation-revolution mixer.
Then, the polymer that side chain is had a functional group is added in the mixture of positive active material and graphene oxide and mixes to form slurry.In the present embodiment, in having the polymer of functional group, side chain adds water and this aqueous solution is added in the mixture of positive active material and graphene oxide and mixes to form slurry.
Note, when needing for the polymer that makes graphene oxide and side chain have functional group reacts to heat or during the interpolation of catalyst etc., carrying out needed processing.
Then, slurry is coated on collector body and carries out drying and form positive electrode active material layer on collector body.In the present embodiment, slurry is coated in on the collector body of aluminium foil manufacturing and carry out the heat drying of 50 ℃ form positive electrode active material layer on collector body.
In addition, also can form sticky end coating (anchor coat layer) before being formed on positive electrode active material layer on collector body on collector body.As the sticky end coating, for example can use the mixture of polymer and conductive auxiliary agent.At this, polymer can use more than one in Kynoar, polyimides, carboxymethyl cellulose and Sodium Polyacrylate.In addition, conductive auxiliary agent can use more than one in acetylene black, carbon black, Graphene, the graphene oxide that is reduced and carbon nano-tube.By utilizing polymer in the sticky end coating can improve adhesion between collector body and positive electrode active material layer, and by utilizing conductive auxiliary agent can reduce contact resistance between collector body and positive electrode active material layer.
In addition, also can carry out surface treatment and the sticky end coating is not set collector body before be formed on positive electrode active material layer on collector body.As surface treatment, such as enumerating etch processes and gold-plated processing etc.By carrying out surface treatment, the collector body surface is formed the concavo-convex complicated shape that waits, can improve the adhesion between collector body and positive electrode active material layer.By improving the adhesion between collector body and positive electrode active material layer, can improve anodal intensity.
Then, the graphene oxide in positive electrode active material layer was also formed the graphene oxide that is reduced originally.Can adopt the method for heat reduction, electrochemical reduction and combined heated reduction and electrochemical reduction etc. as the method for reducing.
In the situation that adopt heat reduction, can reduce by carrying out roasting with baking oven etc.
In the situation that adopt electrochemical reduction, by using collector body and positive electrode active material layer to consist of closed circuit, and positive electrode active material applies the current potential of the current potential of graphene oxide generation reduction reaction or graphene oxide reduction, and graphene oxide is reduced to Graphene.In addition, in the present embodiment, the current potential of graphene oxide generation reduction reaction or the current potential of graphene oxide reduction are called reduction potential.
Particularly, reduce with following method.At first, fill electrolyte in container, then insert, be immersed in electrolyte with positive electrode active material layer with to electrode.Positive electrode active material layer is used as work electrode, and use at least electrode and electrolyte are formed electrochemical cell (opening the loop), the reduction potential that applies graphene oxide by positive electrode active material (work electrode) is reduced to this graphene oxide the graphene oxide that is reduced.In addition, the reduction potential that applies be take to electrode the reduction potential during as benchmark or when in electrochemical cell, reference electrode being set take this reference electrode as benchmark the time reduction potential.For example, when when electrode and reference electrode are used the lithium metal, the reduction potential that applies is the reduction potential (vs.Li/Li take the oxidation-reduction potential of lithium metal as benchmark
+).Reduction current flows through in electrochemical cell (closed circuit) when graphene oxide is reduced.Therefore, by confirming that continuously this reduction current confirms the reduction of graphene oxide, reduction current is considered as lower than the state of fixed value (state that disappears corresponding to the peak value of reduction current) state (state that reduction reaction finishes) that graphene oxide is reduced gets final product.
In addition, when controlling the current potential of positive electrode active material layer, not only can be fixed is the reduction potential of graphene oxide, but also can scan the current potential of the reduction potential that comprises graphene oxide, and this scanning can also be carried out repeatedly.Although notice that the sweep speed of the current potential of positive electrode active material does not limit, more than being preferably 0.005mV/sec and below 1mV/sec.In addition, when scanning the current potential of positive electrode active material layer, both can scan to low potential side from hot side, also can scan to hot side from low potential side.
Although according to the difference of the structure of graphene oxide (functional group have or not etc.) and potential control method (sweep speed etc.), the value of the reduction potential of graphene oxide is slightly different, is roughly 2.0V(vs.Li/Li
+) left and right.Particularly, more than 1.6V and (vs.Li/Li below 2.4V
+) scope in control the current potential of above-mentioned positive electrode active material layer, get final product.
Graphene oxide in positive electrode active material layer also can be made the positive pole of a relevant mode of the present invention originally by above-mentioned operation.
In the present embodiment, with reference to Fig. 3 A and Fig. 3 B, the lithium secondary battery of a relevant mode of the present invention and an example of manufacture method thereof are described.
Fig. 3 A is the outside drawing of Coin shape (single-layer type platypelloid type) lithium secondary battery, and Fig. 3 B is its sectional view.
In Coin shape lithium secondary battery 6000, the anodal tank 6003 that is also used as positive terminal and the cathode pot 6001 that is also used as negative terminal carry out insulated enclosure by the pad 6002 that is formed by polypropylene etc.As mentioned above, anodal 6010 comprise positive electrode collector 6008 and the positive electrode active material layer 6007 that arranges in the mode that is contacted with positive electrode collector 6008.On the other hand, negative pole 6009 comprises negative electrode collector 6004 and the negative electrode active material layer 6005 that arranges in the mode that is contacted with negative electrode collector 6004.Be provided with slider 6006 and electrolyte (not shown) between positive electrode active material layer 6007 and negative electrode active material layer 6005.
As negative electrode collector 6004, can use the electric conducting materials such as titanium, aluminium or stainless steel are formed paper tinsel shape, tabular, netted etc. negative electrode collector.In addition, also the conductive layer that is formed on substrate can be peeled off, and this conductive layer of peeling off is used as negative electrode collector 6004.
Negative electrode active material layer 6005 uses can occlusion and the material that discharges lithium ion on electrochemistry.For example, can use carbon class material, tin, tin oxide, silicon, silica, silicon alloy or the germanium etc. such as lithium, aluminium, carborundum.Perhaps, can use more than one compound in carbon class material, tin, tin oxide, silicon, silica, silicon alloy and germanium such as comprising lithium, aluminium, carborundum.In addition, as can occlusion and discharge the carbon class material of lithium ion, can use Powdered or fibrous graphite or graphite-like carbon.In addition, compare with carbon class material, the occlusion capacity of the lithium ion of silicon, silicon alloy, germanium, lithium, aluminium and tin is large.So, can reduce amount for the material of negative electrode active material layer 6005 by adopting above-mentioned material, so can realize the reduction of cost and the miniaturization of lithium secondary battery 6000.
As slider 6006, can use cellulose (paper), be provided with the polypropylene of emptying aperture or be provided with the insulators such as polyethylene of emptying aperture.
In addition, when using when having sept anodal as anodal 6010, do not need to arrange slider 6006.
As electrolytical solute, use the material with charge carrier ion.As the exemplary of electrolytical solute, can enumerate LiClO
4, LiAsF
6, LiBF
4, LiPF
6, Li(C
2F
5SO
2)
2The lithium salts such as N.
In addition, when the charge carrier ion is alkali metal ion, alkaline-earth metal ions, beryllium ion beyond lithium ion or magnesium ion, also (for example can use alkali metal as electrolytical solute, sodium, potassium etc.), alkaline-earth metal (for example, calcium, strontium, barium etc.), beryllium or magnesium replaces the lithium in above-mentioned lithium salts.
In addition, as electrolytical solvent, use can be carried the material of charge carrier ion.As electrolytical solvent, preferably use aprotic organic solvent.As the exemplary of aprotic organic solvent, can use one or more in ethylene carbonate (EC), propene carbonate, dimethyl carbonate, diethyl carbonate (DEC), γ-butyrolactone, acetonitrile, glycol dimethyl ether, oxolane etc.In addition, when using the macromolecular material of gelation as electrolytical solvent, the fail safe of anti-leakage etc. is improved.And, can realize slimming and the lightweight of lithium secondary battery.As the exemplary of the macromolecular material of gelation, can enumerate silicone adhesive, acrylate glue, acrylonitrile glue, polyethylene glycol oxide, PPOX, fluorine-based polymer etc.In addition, by using one or more to have anti-flammability and difficult volatile ionic liquid (room temperature fuse salt) as electrolytical solvent, even also can prevent the breaking of secondary cell, on fire etc. because the internal short-circuit of secondary cell, the internal temperature such as overcharge rise.
In addition, as electrolyte, can use the solid electrolyte with sulfide-based or oxide-based etc. inorganic material or have the PEO(polyethylene glycol oxide) solid electrolyte of the macromolecular material of class etc.When using solid electrolyte, do not need to arrange sept or slider.In addition, owing to can making cell integrated solidification, so there is no the worry of leakage, fail safe significantly is improved.
As anodal tank 6003, cathode pot 6001, can use metal, the alloy of above-mentioned metal or the alloys (stainless steel etc.) of above-mentioned metal and other metals such as nickel with corrosion resistance, aluminium, titanium.Especially, in order to prevent causing corrosion due to the electrolyte that discharges and recharges of secondary cell, preferably go up nickel plating etc. at corrosion metals (corrosive metal).Anodal tank 6003 is electrically connected to anodal 6010, and cathode pot 6001 is electrically connected to negative pole 6009.
Above-mentioned negative pole 6009, positive pole 6010 and slider 6006 are soaked in electrolyte, and as shown in Fig. 3 B like that, the mode that is arranged on the bottom with anodal tank 6003 stacks gradually positive pole 6010, slider 6006, negative pole 6009, cathode pot 6001, with across the anodal tank 6003 of the mode pressing of pad 6002 and cathode pot 6001, make thus Coin shape lithium secondary battery 6000.
Then, use the structure of Fig. 4 A and Fig. 4 B explanation cylindrical lithium secondary battery.As shown in Fig. 4 A like that, cylindrical lithium secondary battery 7000 has positive cover (battery cover) 7001 at end face, and in the side and the bottom surface have battery can (outer tinning) 7002.Above-mentioned positive cover and battery can (outer tinning) 7002 is by pad (insulation spacer) 7010 insulation.
Fig. 4 B is the figure in the cross section of schematically illustrated cylindrical lithium secondary battery.Interior survey at hollow cylindrical battery can 7002 is provided with cell device, and this cell device is that banded positive pole 7004 and banded negative pole 7006 clip the element that slider 7005 is entwined.Although not shown, cell device is wound centered by centrepin.One end of battery can 7002 is closed and the other end is being opened.Can use metal, the alloy of above-mentioned metal or the alloys (stainless steel etc.) of above-mentioned metal and other metals such as nickel with corrosion resistance, aluminium, titanium as battery can 7002.Especially, cause corrosion, preferably nickel plating etc. on corrosion metals in order to prevent due to the electrolyte that discharges and recharges of secondary cell.In the interior survey of battery can 7002, the cell device of reel positive pole, negative pole and slider is by opposed a pair of insulation board 7008 and 7009 clampings.In addition, the inside that is provided with the battery can 7002 of cell device is injected with electrolyte (not shown).As electrolyte, can use the electrolyte identical with the electrolyte that is used for the Coin shape lithium secondary battery.
Anodal 7004 and negative pole 7006 can utilize with the positive pole of above-mentioned Coin shape lithium secondary battery and the same mode of negative pole and make, but because the positive pole and the negative pole that are used for cylindrical lithium secondary battery are wound, so the difference of cylindrical lithium secondary battery and Coin shape lithium secondary battery is to form active material in the both sides of collector body.By as anodal 7004 positive poles that use execution modes 1 or execution mode 2 to put down in writing, the high secondary cell of capacity that can manufacturer's volume.Anodal 7004 are connected with positive terminal (anodal current collection wire) 7003, and negative pole 7006 is connected with negative terminal (negative pole current collection wire) 7007.Positive terminal 7003 and negative terminal 7007 can use the metal materials such as aluminium.Positive terminal 7003 resistance welded are arrived safety valve mechanism 7012, and with the bottom of negative terminal 7007 resistance welded to battery can 7002.Safety valve mechanism 7012 is passed through PTC(Positive Temperature Coefficient: positive temperature coefficient) element 7011 is electrically connected to positive cover 7001.When the rising of the interior pressure of battery surpassed the threshold value of appointment, safety valve mechanism 7012 was cut off being electrically connected between positive cover 7001 and positive pole 7004.In addition, PTC element 7011 is in the situation that temperature rise to increase the thermo-responsive resistive element of resistance, PTC element 7011 in the situation that resistance increase the restriction magnitude of current and prevent abnormal heating.As the PTC element, can use barium titanate (BaTiO
3) the based semiconductor pottery etc.
In the present embodiment, although as lithium secondary battery, Coin shape and cylindrical lithium secondary battery are shown, can also use the lithium secondary battery of the various shapes such as closed type lithium secondary battery, square lithium secondary battery.In addition, also can adopt the structure that is laminated with a plurality of positive poles, a plurality of negative pole, a plurality of sliders and the structure that is wound with positive pole, negative pole, slider.
Present embodiment can suitably make up with other execution modes and implement.
Can be as the power supply that utilizes power-actuated various electric equipment and electronic equipment according to the lithium secondary battery of a mode of the present invention.
as according to the electric equipment of the lithium secondary battery of a mode of the present invention and the object lesson of electronic equipment, can enumerate television set, the display unit such as monitor, lighting device, desk-top or notebook, word processor, digital versatile disc) reproduction is stored in DVD(Digital Versatile Disc: the still image in recording medium or the image-reproducing means of dynamic image such as, portable CD Player, broadcast receiver, tape recorder, the headphone sound equipment, sound equipment, table clock, wall clock, Subset of cordless telephone, walkie-talkie, portable wireless apparatus, mobile phone, car phone, portable game machine, calculator, portable data assistance, electronic memo, E-book reader, electronic interpreter, the Speech input device, video camera, digital still camera, electric shaver, the high frequency heaters such as microwave oven, electric cooker, washing machine, dust catcher, water heater, electric fan, hair dryer, air-conditioning equipment is such as air conditioner, humidifier and dehumidifier, dishwasher, dish drier, dryer, quilt dryer, refrigerator, the electricity household freezer, the electricity household refrigerator-freezer, the freezing device of nucleic acid preservation, flashlight, the instruments such as chain saw, smoke detector, the Medical Devices such as dialysis apparatus etc.Moreover, can also enumerate industrial equipment such as guiding lamp, semaphore, conveyer belt, escalator, elevator, industrial robot, accumulating system, be used for making the electrical storage device of electric power homogenizing or intelligent grid.In addition, being used to moving body that the electric power from lithium secondary battery advances by motor etc. is also included within the category of electric equipment and electronic equipment.As above-mentioned moving body, such as can enumerate electric automobile (EV), have concurrently internal combustion engine and motor hybrid vehicle (HEV), plug-in hybrid-power automobile (PHEV), use crawler belt to replace the caterpillar of these wheel, the electric bicycle that comprises electrically assisted bicycle, motorcycle, electric wheelchair, golf cart, small-sized or large ship, submarine, helicopter, aircraft, rocket, artificial satellite, space probe, planetary probe, spaceship etc.
In addition, in above-mentioned electric equipment and electronic equipment, the most main power source as being used for supplying power consumption can use the lithium secondary battery according to a mode of the present invention.Perhaps, in above-mentioned electric equipment and electronic equipment, uninterrupted power supply as carrying out when the supply of electric power from above-mentioned main power source or commercial power stops the supply of electric power of electric equipment and electronic equipment can use the lithium secondary battery according to a mode of the present invention.Perhaps, in above-mentioned electric equipment and electronic equipment, as with the accessory power supply that supplies power to electric equipment and electronic equipment that carries out simultaneously from the supply of electric power of above-mentioned main power source or commercial power, can use the lithium secondary battery according to a mode of the present invention.
Fig. 5 illustrates the concrete structure of above-mentioned electric equipment and electronic equipment.In Fig. 5, display unit 8000 is that use is according to an example of the electronic equipment of the lithium secondary battery 8004 of a mode of the present invention.Specifically, display unit 8000 is equivalent to the television broadcasting reception and uses display unit, comprises framework 8001, display part 8002, loud speaker section 8003 and lithium secondary battery 8004 etc.Be arranged on the inside of framework 8001 according to the lithium secondary battery 8004 of a mode of the present invention.Display unit 8000 both can have been accepted the supply of electric power from commercial power, can use the electric power that is accumulated in lithium secondary battery 8004 again.Therefore, even when owing to have a power failure waiting the supply of electric power that to accept from commercial power, by will according to the lithium secondary battery 8004 of a mode of the present invention as uninterrupted power supply, also utilizing display unit 8000.
PlasmaDisplay Panel) and the FED(field-emitter display as display part 8002, can use semiconductor display device such as liquid crystal indicator, possess light-emitting device, electrophoretic display apparatus, the DMD(digital micro-mirror device of the light-emitting components such as organic EL in each pixel: DigitalMicromirrorDevice), the PDP(plasma display:: Field Emission Display) etc.
In addition, except television broadcasting received the display unit of use, display unit also comprised all demonstration information display unit, such as personal computer with display unit or advertisement demonstration with display unit etc.
In Fig. 5, peace edge type lighting device 8100 is that use is according to an example of the electric equipment of the lithium secondary battery 8103 of a mode of the present invention.Specifically, lighting device 8100 comprises framework 8101, light source 8102 and lithium secondary battery 8103 etc.Although example illustrates the situation that lithium secondary battery 8103 is arranged on the inside of the ceiling 8104 that studs with framework 8101 and light source 8102 in Fig. 5, lithium secondary battery 8103 also can be arranged on the inside of framework 8101.Lighting device 8100 both can have been accepted the supply of electric power from commercial power, can use the electric power that is accumulated in lithium secondary battery 8103 again.Therefore, even when owing to have a power failure waiting the supply of electric power that to accept from commercial power, by will according to the lithium secondary battery 8103 of a mode of the present invention as uninterrupted power supply, also utilizing lighting device 8100.
In addition, although example illustrates the peace edge type lighting device 8100 that is arranged on ceiling 8104 in Fig. 5, but both can be used for being arranged on the ceiling 8104 peace edge type lighting device such as sidewall 8105, floor 8106 or window 8107 etc. in addition according to the lithium secondary battery of a mode of the present invention, can be used for desk-top lighting device etc. again.
In addition, as light source 8102, can use the artificial light source that obtains light with utilizing the artificial property of electric power.Specifically, as an example of above-mentioned artificial light source, can enumerate discharge lamp and the light-emitting components such as LED or organic EL such as incandescent lamp bulb, fluorescent lamp.
In Fig. 5, the air conditioner with indoor set 8200 and off-premises station 8204 is that use is according to an example of the electric equipment of the lithium secondary battery 8203 of a mode of the present invention.Specifically, indoor set 8200 comprises framework 8201, air outlet 8202 and lithium secondary battery 8203 etc.Although example illustrates lithium secondary battery 8203 and is arranged on situation in indoor set 8200 in Fig. 5, lithium secondary battery 8203 also can be arranged in off-premises station 8204.Perhaps, also can be provided with lithium secondary battery 8203 in the both sides of indoor set 8200 and off-premises station 8204.Air conditioner both can have been accepted the supply of electric power from commercial power, can use the electric power that is accumulated in lithium secondary battery 8203 again.Especially, when being provided with lithium secondary battery 8203 in the both sides of indoor set 8200 and off-premises station 8204, even when owing to have a power failure waiting the supply of electric power that to accept from commercial power, by being used as uninterrupted power supply according to the lithium secondary battery 8203 of a mode of the present invention, also can utilize air conditioner.
In addition, although example illustrates the detachable air conditioner that is made of indoor set and off-premises station in Fig. 5, also can be with according to the lithium secondary battery of a mode of the present invention integral air conditioner for the function of the function that has indoor set a framework and off-premises station.
In Fig. 5, electric household refrigerator-freezer 8300 is that use is according to an example of the electric equipment of the lithium secondary battery 8304 of a mode of the present invention.Specifically, electric household refrigerator-freezer 8300 comprises framework 8301, refrigerating-chamber door 8302, refrigerating chamber door 8303 and lithium secondary battery 8304 etc.In Fig. 5, lithium secondary battery 8304 is arranged on the inside of framework 8301.Electricity household refrigerator-freezer 8300 both can have been accepted the supply of electric power from commercial power, can use the electric power that is accumulated in lithium secondary battery 8304 again.Therefore, even when owing to have a power failure waiting the supply of electric power that to accept from commercial power, by will according to the lithium secondary battery 8304 of a mode of the present invention as uninterrupted power supply, also utilizing electric household refrigerator-freezer 8300.
In addition, in above-mentioned electric equipment, the electric equipment such as the high frequency heater such as microwave oven and electric cooker needs high power at short notice.Therefore, by being used for according to the secondary lithium batteries of a mode of the present invention the accessory power supply of the electric power that the auxiliary commerce power supply can not ample supply, can prevent the master switch tripping operation of commercial power when using electric equipment.
In addition, in the time period of not using electric equipment and electronic equipment, especially in the time period that the ratio of the electric weight of the actual use in total electric weight that the source of supply of commercial power can be supplied (being called the power utilization rate) is low, electric power is accumulated in lithium secondary battery, can be suppressed at thus that in the time period beyond the above-mentioned time period, the electricity usage rate increases.For example, low and do not carry out night of the switch of refrigerating-chamber door 8302 or refrigerating chamber door 8303 at temperature when being electric household refrigerator-freezer 8300, electric power is accumulated in lithium secondary battery 8304.And, high and carry out daytime of the switch of refrigerating-chamber door 8302 or refrigerating chamber door 8303 at temperature, lithium secondary battery 8304 as accessory power supply, can be suppressed the electricity usage rate on daytime thus.
Present embodiment can suitably make up with other execution modes and implement.
Execution mode 5
Then, use Fig. 6 A to Fig. 6 C that the portable data assistance as an example of electronic equipment is described.
Fig. 6 A and Fig. 6 B are the dull and stereotyped terminals that can carry out folding.Fig. 6 A is open mode, and dull and stereotyped terminal comprises framework 9630, display part 9631a, display part 9631b, display mode diverter switch 9034, mains switch 9035, battery saving mode diverter switch 9036, clamp 9033 and console switch 9038.
In display part 9631a, its part can be used as the regional 9632a of touch-screen, and can input data by touching shown operation keys 9638.In addition, in display part 9631a, the zone that half is shown as an example only has Presentation Function and second half zone to have the structure of the function of touch-screen, but is not limited to this structure.Also can adopt the whole zone of display part 9631a to have the structure of the function of touch-screen.For example, whole the display keyboard button of display part 9631a come used as touch-screen, and display part 9631b is used as display panel.
In addition, also same with display part 9631a in display part 9631b, the part of display part 9631b can be used as the regional 9632b of touch-screen.In addition, point, show the position that keyboard shows switching push button 9639 on the touch touch-screen such as screen touch pen by use, can be on display part 9631b the display keyboard button.
In addition, also can touch simultaneously input to the regional 9632a of touch-screen and the regional 9632b of touch-screen.
In addition, display mode diverter switch 9034 can be erected screen display and shown switching and white and black displays and the colored switching that shows etc. of showing etc. the direction that shows with horizontal screen display.The light quantity of the outer light during use that battery saving mode diverter switch 9036 can go out according to the light sensors that is built-in with by dull and stereotyped terminal and display brightness is set as optimal brightness.Dull and stereotyped terminal can also be built-in with other checkout gears of sensor that gyroscope, acceleration transducer etc. detect gradient except optical sensor.
In addition, although Fig. 6 A illustrates the display part 9631b example identical with the display area of display part 9631a, be not limited to this, a side size can be different from the opposing party's size, and their display quality also can be variant.For example can adopt a side to compare the display floater that can carry out the demonstration of fine with the opposing party.
Fig. 6 B closes to close state, and dull and stereotyped terminal comprises framework 9630, solar cell 9633, charge-discharge control circuit 9634, battery 9635 and DCDC transducer 9636.In addition, in Fig. 6 B, the structure that has battery 9635, DCDC transducer 9636 as an example of charge-discharge control circuit 9634 is shown, and battery 9635 has illustrated in the above-described embodiment lithium secondary battery.
In addition, dull and stereotyped terminal can fold, the framework 9630 of can closing when therefore not using.Therefore, can protect display part 9631a, display part 9631b, so can provide the good and reliability of a kind of durability from the viewpoint of long-term use also good dull and stereotyped terminal.
In addition, the dull and stereotyped terminal shown in Fig. 6 A and Fig. 6 B can also have following function: show various information (still image, dynamic image, character image etc.); Calendar, date or the moment etc. are presented on display part; The information that is presented on display part is carried out touch operation or editor's touch input; Control processing etc. by various softwares (program).
Be arranged on the solar cell 9633 on the surface of dull and stereotyped terminal by utilization, can supply power to touch-screen, display part or picture signal handling part etc.In addition, solar cell 9633 can be arranged on a face or two faces of framework 9630, solar cell 9633 can charge to battery 9635 efficiently thus.In addition, when the lithium secondary battery that uses as battery 9635 according to a mode of the present invention, the advantage that can realize miniaturization etc. is arranged.
In addition, structure and the work to the charge-discharge control circuit 9634 shown in Fig. 6 B describes with reference to the block diagram shown in Fig. 6 C.Fig. 6 C illustrates solar cell 9633, battery 9635, DCDC transducer 9636, transducer 9637, switch SW 1 to SW3 and display part 9631, the charge-discharge control circuit 9634 shown in battery 9635, DCDC transducer 9636, transducer 9637 and switch SW 1 to SW3 corresponding diagram 6B.
At first, the example of the work when light is generated electricity by solar cell 9633 outside utilizing is described.Utilize the voltage of 9636 pairs of solar cell electricity power of DCDC transducer to boost or step-down so that it becomes voltage that battery 9635 is charged.And, when utilizing solar cell 9633 electricity power to make display part 9631 work, make switch SW 1 conducting and utilize transducer 9637 with the boost in voltage of this electric power or be depressured to the needed voltage of display part 9631.In addition, when the demonstration do not carried out on display part 9631, SW1 is ended and the SW2 conducting is charged to battery 9635.
In addition, although an example as generator unit illustrates solar cell 9633, but be not limited to this, also can use other generator units such as piezoelectric element (piezoelectric element) or thermoelectric conversion element (Peltier element (peltier element)) that battery 9635 is charged.For example, also can adopt: receive and dispatch in the mode of wireless (noncontact) the noncontact electric power transfer module that electric power charges; Or make up the structure that other charhing units charge.
In addition, as long as possess the illustrated lithium secondary battery of above-mentioned execution mode, certainly be not limited to the electric equipment shown in Fig. 6 A to Fig. 6 C.
Execution mode 6
Moreover, with reference to the moving body of an example of Fig. 7 A and Fig. 7 B explanation electric equipment and electronic equipment.
Lithium secondary battery that can execution mode 1 to 3 is illustrated is used for controlling uses battery.By utilizing plug-in part technology or non-contact power to come and to charge with battery to controlling from outside supply capability.In addition, when moving body is railways motor-car railway carriage or compartment, can charge from aerial cable or conductor rail supply capability.
Fig. 7 A and Fig. 7 B illustrate an example of electric automobile.Electric automobile 9700 is equipped with lithium secondary battery 9701.Utilize control circuit 9702 adjust lithium secondary batteries 9701 electric power output and supply to drive unit 9703.Control circuit 9702 is controlled by the processing unit 9704 with not shown ROM, RAM, CPU etc.
Use separately DC motor or alternating current motor as drive unit 9703, perhaps be used in combination motor and internal combustion engine.Processing unit 9704 is according to the input message of the driver's of electric automobile 9700 operation information (accelerate, slow down, stop etc.), running information (information in upward trend or downhill path etc., be applied to the information on load of driving wheel etc.), to control circuit 9702 output control signals.The electric energy that control circuit 9702 is supplied with from lithium secondary battery 9701 according to the control signal adjustment of processing unit 9704 and the output of accessory drive 9703.When alternating current motor is installed, although not shown, the built-in inverter that direct current is converted to interchange also.
By utilizing plug-in part technology can charge to lithium secondary battery 9701 from outside supply capability.For example, charge to lithium secondary battery 9701 by supply socket from commercial power.Can will be that the direct current constant voltage with constant voltage values charges from the voltage transitions of the electric power of outside by conversion equipments such as AC/DC transducers.By lithium secondary battery according to a mode of the present invention being installed as lithium secondary battery 9701, can shorten the charging interval etc., thereby can improve convenience.In addition, discharge and recharge speed by raising, can improve the accelerative force of electric automobile 9700, and can improve the performance of electric automobile 9700.In addition, when can realize the miniaturization and of lithium secondary battery 9701 itself by the characteristic that improves lithium secondary battery 9701 time, the lightweight of vehicle can be realized, also fuel consumption can be reduced.
Present embodiment can suitably make up with other execution modes and implement.
In the present embodiment, the polymer that has a functional group as side chain is made positive pole with many arylamine and as adhesive with many arylamine and the reactant that the graphene oxide that is reduced forms covalent bond.Moreover, use lithium metal and carry out the assessment of above-mentioned positive pole as negative pole.
" anodal manufacturing "
＜side chain has the polymer of functional group 〉
The operating weight mean molecule quantity is many arylamine (LTD. makes for PAA-15C, NITTOBOMEDICAL CO.) of 15000.
＜graphene oxide 〉
Make graphene oxide by Modified Hummers legal system.Particularly, add the sulfuric acid solution, aquae hydrogenii dioxidi etc. of potassinm permanganate and cause oxidation reaction in the single crystal graphite powder, making the dispersion liquid that contains graphene oxide.
＜LiFePO4 〉
Then, make LiFePO4.In the manufacturing of LiFePO4, at first as the raw material of LiFePO4, use lithium carbonate (Li
2CO
3), ferric oxalate (II) dihydrate (FeC
2O
42H
2O) and ammonium dihydrogen phosphate (NH
4H
2PO
4), above-mentioned substance is carried out weighing and makes its mol ratio is Li:Fe:P=1:1:1, mixes and process by the first ball mill.Note, lithium carbonate is for the raw material of introducing lithium, and ferric oxalate (II) dihydrate is for the raw material of introducing iron, and ammonium dihydrogen phosphate is for the raw material of introducing phosphoric acid.In the present embodiment, as the raw material of LiFePO4, the lithium carbonate, ferric oxalate (II) dihydrate and the ammonium dihydrogen phosphate that use impurity concentration to be lowered respectively.
Adding acetone as solvent, rotation number is 300rpm, and rotational time is 2 hours, and sphere diameter φ carries out the first ball mill under the condition of 3mm to process.In addition, as ball grinder (ballmill pot) (cylindrical container) and ball, use zirconium matter ball grinder and zirconium matter ball.
Then, powder is carried out the first heat treatment (preroast).Under blanket of nitrogen, with 350 ℃, powder is carried out first heat treatment of 10 hours.
After carrying out the first heat treatment, use mortar that burned material is pulverized.Then, by the second ball mill processing, the burned material of pulverizing is further pulverized.
Adding acetone as solvent, rotation number is 300rpm, and rotational time is 2 hours, and sphere diameter φ carries out the second ball mill under the condition of 3mm to process.
Then, powder is carried out the second heat treatment (main roasting).Under blanket of nitrogen, with 600 ℃, powder is carried out second heat treatment of 1 hour.
After carrying out the second heat treatment, use mortar that burned material is pulverized.
＜manufacturing of positive electrode active material layer 〉
The powder of the powder of the LiFePO4 by above-mentioned operation manufacturing, graphene oxide and many arylamine are carried out weighing and make its weight ratio is LiFePO4: graphene oxide: many arylamine=97.822:2.104:0.074.
Then, add water in LiFePO4 and graphene oxide and also carry out wet mixed with the rotation-revolution mixer with 2000rpm.
Then, the many virtues of preparation by the 0.153wt% aqueous solution and it is added to the mixture of LiFePO4 and graphene oxide, and mix and form slurry.
Then, add the water adjusting viscosity in slurry, this slurry is coated in on the collector body of aluminium foil manufacturing and carry out the heat drying of 50 ℃ form positive electrode active material layer on collector body.Then, graphene oxide is reduced to 170 ℃ of heating that this collector body and positive electrode active material layer were carried out 10 hours the graphene oxide that is reduced, forms thus the positive pole of the present embodiment.
" characteristic of secondary cell "
Use the positive pole of making by above-mentioned operation to make secondary cell.Use the elementary cell of the Japanese limited Tomcell of commercial firm manufacturing as the unit.Use lithium metal as negative pole.Use the 1.0mol/L aqueous solution (LiPF that lithium hexafluoro phosphate is dissolved in ethylene carbonate as electrolyte
6EC) and the mixture of diethyl carbonate (DEC), its blending ratio is LiPF
6The EC:DEC=1:1(volume ratio).Use polypropylene as sept.
With following condition, the secondary cell of making is measured the constant current charge-discharge characteristic.
Charging: 0.2C(CCCV), upper voltage limit 4.3[V], lower bound current value 0.01C during CV
Discharge: 0.2C(CC)
Fig. 8 A and Fig. 8 B illustrate resulting charging and discharging curve.Fig. 8 A and Fig. 8 B are the charging and discharging curves with identical conditions manufacturing and two secondary cells measuring.The longitudinal axis represents voltage, and transverse axis represents capacity.Solid line in accompanying drawing represents charging, and dotted line represents discharge.
All confirm broad flat region (plateau region) in the accompanying drawing of two secondary cells shown in Fig. 8 A and Fig. 8 B, this means that the positive pole of the present embodiment normally discharges and recharges.
Comparative example 1
In this comparative example, only make positive pole with the graphene oxide that is reduced as adhesive.Moreover, use lithium metal and carry out the assessment of above-mentioned positive pole as negative pole.
" anodal manufacturing "
＜manufacturing of positive electrode active material layer 〉
Prepare similarly to Example 1 graphene oxide and LiFePO4, the powder of the powder of LiFePO4 and graphene oxide is carried out weighing and makes its weight ratio is LiFePO4: graphene oxide=95:5.
Then, also carrying out wet mixed with the rotation-revolution mixer with 2000rpm forms slurry to add water in LiFePO4 and graphene oxide.
Then, slurry is coated in forms positive electrode active material layer on collector body similarly to Example 1, and this collector body and positive electrode active material layer are carried out drying and reduction processing, form thus the positive pole of this comparative example.
" characteristic of secondary cell "
Measure similarly to Example 1 charge-discharge characteristic.Fig. 9 A and Fig. 9 B illustrate charging and discharging curve.Fig. 9 A and Fig. 9 B are the charging and discharging curves with identical conditions manufacturing and two secondary cells measuring.Solid line in accompanying drawing represents charging, and dotted line represents discharge.
All confirm the flat region in the accompanying drawing of two secondary cells shown in Fig. 9 A and Fig. 9 B, this means that the positive pole of this comparative example normally discharges and recharges.
In addition, Figure 10 illustrates the comparison of charging and discharging curve of Fig. 9 A of the charging and discharging curve of Fig. 8 A of embodiment 1 and comparative example 1.Solid line in accompanying drawing represents charging, and dotted line represents discharge.In addition, the longitudinal axis represents voltage, and transverse axis represents capacity.The transverse axis of Figure 10 illustrates the following scope of the above 180mAh/g of 100mAh/g of enlarged drawing 8A and Fig. 9 A.
As shown in Figure 10, compare with the positive pole of comparative example 1 in the curve of the positive pole of embodiment 1 and confirm broader flat region.
According to embodiment 1 and comparative example 1 more as can be known, the reactant by the polymer that uses side chain to have functional group as adhesive is combined with the graphene oxide that is reduced can enlarge the flat region in charging and discharging curve, can improve charge-discharge characteristic thus.
In the present embodiment, make positive pole as adhesive with the graphene oxide that is reduced and the reactant of polymer covalent bond.Moreover, use graphite and carry out the assessment of above-mentioned positive pole as negative pole.
" anodal manufacturing "
Make similarly to Example 1 anodal.The thickness of positive electrode active material layer is 25 μ m, and the weight of positive active material is 5.69mg, and electrode density is 2.06g/cm
3
" characteristic of secondary cell "
Use the positive pole of making by above-mentioned operation to make secondary cell.Use the elementary cell of the Japanese limited Tomcell of commercial firm manufacturing as the unit.
Use graphite as negative pole.Specifically, use the mixture of graphite (particle diameter is the carbonaceous mesophase spherules (MCMB) of 9 μ m), acetylene black (AB) and Kynoar (PVDF), its blending ratio is graphite: the AB:PVDF=93:2:5(weight ratio).The thickness of negative electrode active material layer is 62 μ m, and the weight of negative electrode active material is 11.2mg, and electrode density is 1.54g/cm
3
Use the 1.0mo l/L aqueous solution (LiPF that lithium hexafluoro phosphate is dissolved in ethylene carbonate as electrolyte
6EC) and the mixture of diethyl carbonate (DEC), blending ratio is LiPF
6The EC:DEC=1:1(volume ratio).Use polypropylene as sept.
With following condition, the secondary cell of making is measured the constant current charge-discharge characteristic.
Charging: 0.2C(CCCV), upper voltage limit 4.3[V], lower bound current value 0.01C during CV
Discharge: 0.2C(CC)
Figure 11 illustrates resulting charging and discharging curve.The longitudinal axis represents voltage, and transverse axis represents capacity.Solid line in accompanying drawing represents charging, and dotted line represents discharge.
As shown in Figure 11, even use graphite as negative pole, the positive pole of the reactant that the polymer that uses side chain to have functional group as adhesive is combined with the graphene oxide that is reduced also normally discharges and recharges.
In the present embodiment, make the reactant that many arylamine are combined with graphene oxide and the combination of many arylamine and graphene oxide is assessed.
＜manufacturing of reactant 〉
Add water and form the graphene oxide aqueous dispersions in the graphene oxide 200mg that makes similarly to Example 1.Add the aqueous solution of arylamine more than 1.5% 1g in this dispersion liquid, obtained the brown sediment.Wash by this sediment of filtered and recycled and water, then carry out drying under reduced pressure, obtain thus reactant.
〈FT-IR〉
Figure 12 and Figure 13 illustrate the result of FT-IR spectrum of the graphene oxide of the reactant of the graphene oxide of measuring manufacturing and many arylamine and raw material thereof.IR adopts KBr (KBr) pressed disc method to carry out.Transverse axis represents wave number, and the longitudinal axis represents transmitance.It is 400cm that Figure 12 illustrates wave number
-1To 4000cm
-1The spectrum of scope, Figure 13 illustrates the 900cm that enlarges in Figure 12
-1To 1900cm
-1The spectrum of scope, the difference of the spectrum of reactant and graphene oxide is large in this scope.Figure 13 illustrates the ownership of the peak value of each spectrum.
Compare with graphene oxide, the peak value of epoxy radicals of resulting from of reactant significantly reduces.Hence one can see that compares with graphene oxide, and the epoxy radicals in reactant reduces.
In addition, compare the 1050cm of reactant with graphene oxide
-1Near the peak value that INFRARED ABSORPTION is shown is wider.Can think that this wide zone comprises results from the INFRARED ABSORPTION of C-N key.
These results illustrate by the amino in the epoxy radicals in graphene oxide and many arylamine, and graphene oxide and many arylamine form the C-N key.
In the present embodiment, graphene oxide was also originally formed the graphene oxide that is reduced and it was assessed.
" manufacturing of graphene oxide "
Make graphene oxide by single crystal graphite similarly to Example 1, this graphene oxide is coated in on the collector body of aluminium foil manufacturing and carry out sample 1A and the sample 1B that drying manufacturing has graphene oxide.
" reduction of graphene oxide "
Then, sample 1A with graphene oxide and sample 1B are carried out sample 2A and the sample 2B that electrochemical reduction or heat reduction manufacturing have the graphene oxide that is reduced.
＜electrochemical reduction 〉
＜heat reduction 〉
《XPS》
Utilize XPS to carry out the assessment of bonding state and element composition to sample 1A, sample 1B, sample 2A and sample 2B.
＜bonding state 〉
Figure 14 illustrates and utilizes XPS mensuration as the comparison of the bonding state of the single crystal graphite of raw material, the sample 1A with graphene oxide and sample 1B, the sample 2A with the graphene oxide that is reduced and sample 2B.The longitudinal axis illustrates the ratio of each combination with percentage.Carry out by the displacement to the peak value that utilizes the carbon that XPS obtains the ratio that wave analysis is calculated each combination.
About the bonding state of single crystal graphite, 99.3% is that (the π key between carbon atom is also referred to as sp to the C=C key
2Track).
Do not comprise the C=C key at the sample 1A with graphene oxide and sample 1B, its bonding state is any in O=C-O key, C=O key, C-O key, C-C key and c h bond.Carbon atom in hence one can see that Graphene is mostly because oxidation loses the C=C key.
On the other hand, the sample 2A with the graphene oxide that is reduced and the sample 2B through electrochemical reduction or heat reduction comprises the C=C key.In addition, the shared ratio of C=C key is more than 44.1% in the summation of O=C-O key, C=O key, C-O key, C-C key, c h bond, C=C key.Hence one can see that, and the carbon atom in graphene oxide is because reduction forms the C=C key.
According to the above results as can be known, even any method in employing electrochemical reduction and heat reduction, graphene oxide also forms C=C key (the π key between carbon atom).In other words, the graphene oxide that is reduced can be described as the graphene oxide with C=C key.In addition, can also say that in the summation of O=C-O key, C=O key, C-O key, C-C key, c h bond, the C=C key shared ratio of C=C key is the graphene oxide more than 5%, more than 10% or more than 30%.
＜element composition 〉
Figure 15 illustrates the comparison that the surface-element with the same sample of Figure 14 that utilizes that XPS measures forms.The longitudinal axis illustrates atom %.
In single crystal graphite, the ratio of carbon atom is 98.5 atom %, and the ratio of oxygen atom is 1.5 atom %.
The sample 1A and the sample 1B that comprise the graphene oxide that the single crystal graphite oxidation is formed comprise more oxygen atom, and its ratio is more than 28.8 atom %.
With respect to this, in the sample 2A and sample 2B that carry out the graphene oxide that having of electrochemical reduction or heat reduction be reduced, the ratio of oxygen atom reduces, and its ratio is below 14.8 atom %.
According to the above results as can be known, even any method in employing electrochemical reduction and heat reduction also can be reduced to the ratio of oxygen atom below 15 atom %.The ratio of the oxygen atom in the graphene oxide that in other words, is reduced is below 15 atom %.
Claims (14)
1. anode of secondary cell comprises:
Positive electrode active material layer on collector body,
Wherein, described positive electrode active material layer comprises:
A plurality of particle shape positive active materials;
Graphene oxide; And
The polymer that has functional group as side chain, this polymer is combined with described graphene oxide,
And at least a portion of described graphene oxide contacts with at least one in described a plurality of particle shape positive active materials.
2. anode of secondary cell according to claim 1, wherein said positive active material comprises lithium and phosphorus, and described positive active material also comprises iron or manganese.
3. anode of secondary cell according to claim 1, wherein said functional group is amino.
4. anode of secondary cell according to claim 1, the wherein said polymer that has a functional group as side chain are any in many arylamine, polyimides and polyamide-imides.
5. anode of secondary cell according to claim 1, wherein said polymer and described graphene oxide form covalent bond.
6. anode of secondary cell according to claim 1, the carbon atom of wherein said graphene oxide and the nitrogen-atoms of described polymer are bonded to each other.
7. anode of secondary cell according to claim 1, also comprise the sticky end coating between described collector body and described positive electrode active material layer.
8. anode of secondary cell according to claim 7, wherein said sticky end coating comprises mixture, this mixture comprises: one or more in Kynoar, polyimides, carboxymethyl cellulose and Sodium Polyacrylate; And one or more in acetylene black, carbon black, Graphene, the graphene oxide that is reduced and carbon nano-tube.
9. secondary cell comprises:
Positive pole according to claim 1;
Negative pole; And
Slider between described positive pole and described negative pole.
10. the manufacture method of an anode of secondary cell comprises:
Mix a plurality of particle shape positive active materials, graphene oxide and water;
Described mixture interpolation aqueous solutions of polymers to described a plurality of particle shape positive active materials, described graphene oxide and described water is made slurry;
Described slurry is coated on collector body;
Described slurry is carried out drying form positive electrode active material layer; And
With the described graphene oxide reduction in described positive electrode active material layer.
11. the manufacture method of anode of secondary cell according to claim 10, wherein by soak described collector body and to the electrolyte of electrode in the reduction of described graphene oxide during the current potential of the described graphene oxide generation reduction reaction of described collector body supply is carried out described positive electrode active material layer.
12. the manufacture method of anode of secondary cell according to claim 10 wherein is reduced by the described graphene oxide that heats in described positive electrode active material layer.
13. the manufacture method of anode of secondary cell according to claim 10 also comprises: before being coated in described slurry on described collector body, described collector body is carried out surface treatment.
14. the manufacture method of anode of secondary cell according to claim 10, wherein said positive active material comprises lithium and phosphorus, and described positive active material also comprises iron or manganese.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011282925 | 2011-12-26 | ||
| JP2011-282925 | 2011-12-26 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103178239A true CN103178239A (en) | 2013-06-26 |
| CN103178239B CN103178239B (en) | 2018-02-23 |
Family
ID=48637962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210571579.8A Expired - Fee Related CN103178239B (en) | 2011-12-26 | 2012-12-25 | The manufacture method of anode of secondary cell and anode of secondary cell |
Country Status (4)
| Country | Link |
|---|---|
| US (3) | US20130164619A1 (en) |
| JP (1) | JP6009343B2 (en) |
| KR (3) | KR102093094B1 (en) |
| CN (1) | CN103178239B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105489898A (en) * | 2015-12-31 | 2016-04-13 | 深圳市贝特瑞新能源材料股份有限公司 | Conductive waterborne binder and preparation method therefor, and lithium ion battery |
| CN107425199A (en) * | 2016-05-23 | 2017-12-01 | 中南大学 | A kind of conduction leads lithium difunctionalization graphene oxide composite material and preparation method thereof and the application in lithium sulphur or lithium-air battery |
| CN107768670A (en) * | 2017-10-23 | 2018-03-06 | 东莞理工学院 | Positive electrode material, preparation method and application, positive electrode preparation method |
| CN110010848A (en) * | 2014-01-28 | 2019-07-12 | 株式会社Lg化学 | Surface-coated positive electrode active material, method for preparing same, and positive electrode and lithium secondary battery comprising same |
| CN114864935A (en) * | 2022-04-19 | 2022-08-05 | 中国科学院过程工程研究所 | Method for preparing high-rate lithium battery negative electrode material from natural graphite spherical tailings |
Families Citing this family (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6035013B2 (en) | 2011-08-30 | 2016-11-30 | 株式会社半導体エネルギー研究所 | Electrode fabrication method |
| JP2013054878A (en) | 2011-09-02 | 2013-03-21 | Semiconductor Energy Lab Co Ltd | Method of manufacturing electrode and power storage device |
| US9384904B2 (en) | 2012-04-06 | 2016-07-05 | Semiconductor Energy Laboratory Co., Ltd. | Negative electrode for power storage device, method for forming the same, and power storage device |
| JP6216154B2 (en) | 2012-06-01 | 2017-10-18 | 株式会社半導体エネルギー研究所 | Negative electrode for power storage device and power storage device |
| KR102195511B1 (en) | 2012-11-07 | 2020-12-28 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Electrode for power storage device, power storage device, and manufacturing method of electrode for power storage device |
| JP6159228B2 (en) | 2012-11-07 | 2017-07-05 | 株式会社半導体エネルギー研究所 | Method for producing positive electrode for non-aqueous secondary battery |
| JP6586269B2 (en) | 2013-10-22 | 2019-10-02 | 株式会社半導体エネルギー研究所 | Electrode for power storage device |
| KR101693930B1 (en) * | 2013-10-24 | 2017-01-09 | 한양대학교 산학협력단 | Fabricating method of electrode for electrochemical device, electrode slurry, and electrode for electrochemical device fabricated thereby |
| WO2015080305A1 (en) * | 2013-11-27 | 2015-06-04 | 주식회사 엘지화학 | Electrode assembly and electrochemical device including same |
| JP2016013958A (en) | 2013-12-02 | 2016-01-28 | 株式会社半導体エネルギー研究所 | Device and film manufacturing method |
| GB2521193A (en) * | 2013-12-12 | 2015-06-17 | Nokia Technologies Oy | Electronic apparatus and associated methods |
| CN111403683B (en) * | 2014-03-13 | 2024-02-23 | 株式会社半导体能源研究所 | Electrode, power storage device, electronic apparatus, and method for manufacturing electrode |
| JP6631012B2 (en) * | 2014-03-27 | 2020-01-15 | 東レ株式会社 | Method for producing lithium-rich cathode active material composite particles |
| JP6609548B2 (en) * | 2014-04-11 | 2019-11-20 | 株式会社エンビジョンＡｅｓｃエナジーデバイス | Secondary battery |
| US9847151B2 (en) * | 2014-07-08 | 2017-12-19 | King Abdulaziz University | Method of making and using flexible elastic nanotube composite |
| JP6666107B2 (en) * | 2014-10-24 | 2020-03-13 | 株式会社半導体エネルギー研究所 | Method for producing storage battery electrode, and storage battery electrode |
| US20160118666A1 (en) * | 2014-10-24 | 2016-04-28 | Semiconductor Energy Laboratory Co., Ltd. | Storage battery electrode, manufacturing method thereof, storage battery, and electronic device |
| KR102266779B1 (en) | 2014-12-26 | 2021-06-21 | 엘지디스플레이 주식회사 | Conductive film, method for fabricating the same and display device having conductive film |
| JP6602786B2 (en) | 2015-01-09 | 2019-11-06 | 株式会社半導体エネルギー研究所 | Method for producing electrode for storage battery |
| CN105098239A (en) * | 2015-04-29 | 2015-11-25 | 宁波职业技术学院 | Graphene lithium ion battery electrolyte |
| WO2016178117A1 (en) | 2015-05-06 | 2016-11-10 | Semiconductor Energy Laboratory Co., Ltd. | Secondary battery and electronic device |
| JP2016222526A (en) | 2015-05-29 | 2016-12-28 | 株式会社半導体エネルギー研究所 | Film formation method and element |
| JP2017045726A (en) | 2015-08-27 | 2017-03-02 | 株式会社半導体エネルギー研究所 | Electrode, manufacturing method thereof, storage battery, and electronic device |
| WO2017066581A1 (en) * | 2015-10-14 | 2017-04-20 | Northwestern University | Graphene-coated metal oxide spinel cathodes |
| KR20250026886A (en) | 2016-07-05 | 2025-02-25 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Positive electrode active material, method for manufacturing positive electrode active material, and secondary battery |
| US20180076489A1 (en) * | 2016-09-12 | 2018-03-15 | Semiconductor Energy Laboratory Co., Ltd. | Electrode and power storage device |
| DE202017007622U1 (en) | 2016-10-12 | 2023-09-13 | Semiconductor Energy Laboratory Co., Ltd. | Positive electrode active material particles |
| KR102685436B1 (en) * | 2017-05-03 | 2024-07-15 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Manufacturing method of positive active material particles and secondary battery |
| KR20230167132A (en) | 2017-05-12 | 2023-12-07 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Positive electrode active material particles |
| KR102645512B1 (en) | 2017-05-19 | 2024-03-07 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Positive electrode active material, method for manufacturing positive electrode active material, and secondary battery |
| KR20230146129A (en) | 2017-06-26 | 2023-10-18 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Method for manufacturing positive electrode active material, and secondary battery |
| CN112909239B (en) | 2018-11-06 | 2023-03-24 | Sk新能源株式会社 | Positive electrode active material for lithium secondary battery and method for manufacturing same |
| US11094929B2 (en) * | 2019-05-06 | 2021-08-17 | City University Of Hong Kong | Energy storage device, an electrode for an energy storage device, and a method of fabricating the electrode |
| CN112289989A (en) * | 2020-10-12 | 2021-01-29 | 常州高态信息科技有限公司 | Ultralow-temperature lithium iron phosphate lithium ion battery |
| WO2022258212A1 (en) * | 2021-06-11 | 2022-12-15 | INBRAIN Neuroelectronics S.L. | Neurostimulation system for deep brain stimulation |
| CN118109140B (en) * | 2024-04-30 | 2024-07-16 | 安徽理士新能源发展有限公司 | Conductive composite adhesive, preparation method, electrode plate and application |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050186378A1 (en) * | 2004-02-23 | 2005-08-25 | Bhatt Sanjiv M. | Compositions comprising carbon nanotubes and articles formed therefrom |
| CN101243566A (en) * | 2005-09-06 | 2008-08-13 | Lg化学株式会社 | Composite binder containing carbon nanotube and lithium secondary battery employing the same |
| CN101710619A (en) * | 2009-12-14 | 2010-05-19 | 重庆大学 | Electrode plate for lithium ion battery and manufacturing method thereof |
| CN102077392A (en) * | 2009-01-26 | 2011-05-25 | 丰田自动车株式会社 | Positive electrode for lithium secondary battery and use thereof |
| WO2011079238A1 (en) * | 2009-12-24 | 2011-06-30 | Aruna Zhamu | Conductive graphene polymer binder for electrochemical cell electrodes |
Family Cites Families (46)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0660870A (en) | 1992-08-05 | 1994-03-04 | Toshiba Battery Co Ltd | Manufacture of dry battery |
| EP0662728B1 (en) * | 1993-12-29 | 1998-04-29 | TDK Corporation | Lithium secondary cell |
| JPH1125983A (en) | 1997-07-04 | 1999-01-29 | Japan Storage Battery Co Ltd | Active material for lithium battery |
| JP4567822B2 (en) | 1999-03-24 | 2010-10-20 | 株式会社東芝 | Square non-aqueous electrolyte secondary battery |
| JP4124694B2 (en) | 2003-05-02 | 2008-07-23 | 日立マクセル株式会社 | Coin type non-aqueous secondary battery |
| US7842432B2 (en) | 2004-12-09 | 2010-11-30 | Nanosys, Inc. | Nanowire structures comprising carbon |
| US7939218B2 (en) | 2004-12-09 | 2011-05-10 | Nanosys, Inc. | Nanowire structures comprising carbon |
| US8278011B2 (en) | 2004-12-09 | 2012-10-02 | Nanosys, Inc. | Nanostructured catalyst supports |
| CN101107737B (en) | 2004-12-09 | 2012-03-21 | 奈米系统股份有限公司 | Nanowire-based membrane electrode assemblies for fuel cells |
| JP3850427B2 (en) | 2005-03-22 | 2006-11-29 | 株式会社物産ナノテク研究所 | Carbon fiber bonded body and composite material using the same |
| JP3958781B2 (en) | 2005-07-04 | 2007-08-15 | 昭和電工株式会社 | Negative electrode for lithium secondary battery, method for producing negative electrode composition, and lithium secondary battery |
| WO2007004728A1 (en) | 2005-07-04 | 2007-01-11 | Showa Denko K.K. | Method for producing anode for lithium secondary battery and anode composition, and lithium secondary battery |
| WO2008048295A2 (en) | 2005-11-18 | 2008-04-24 | Northwestern University | Stable dispersions of polymer-coated graphitic nanoplatelets |
| AU2006318658B2 (en) | 2005-11-21 | 2011-07-28 | Nanosys, Inc. | Nanowire structures comprising carbon |
| KR100836524B1 (en) | 2006-02-23 | 2008-06-12 | 한국전기연구원 | Active Material Having High Capacitance For An Electrode, Manufacturing Method thereof, Electrode And Energy Storage Apparatus Comprising The Same |
| KR100923304B1 (en) | 2007-10-29 | 2009-10-23 | 삼성전자주식회사 | Graphene sheet and process for preparing the same |
| US7745047B2 (en) | 2007-11-05 | 2010-06-29 | Nanotek Instruments, Inc. | Nano graphene platelet-base composite anode compositions for lithium ion batteries |
| KR101267351B1 (en) | 2007-12-25 | 2013-05-24 | 가오 가부시키가이샤 | Composite material for positive electrode of lithium battery |
| JP5377946B2 (en) | 2007-12-25 | 2013-12-25 | 花王株式会社 | Composite material for lithium battery positive electrode |
| EP2276698A1 (en) | 2008-04-14 | 2011-01-26 | Dow Global Technologies Inc. | Lithium metal phosphate/carbon nanocomposites as cathode active materials for secondary lithium batteries |
| US9991391B2 (en) * | 2008-07-25 | 2018-06-05 | The Board Of Trustees Of The Leland Stanford Junior University | Pristine and functionalized graphene materials |
| US8257867B2 (en) | 2008-07-28 | 2012-09-04 | Battelle Memorial Institute | Nanocomposite of graphene and metal oxide materials |
| US8821763B2 (en) | 2008-09-30 | 2014-09-02 | Tdk Corporation | Active material and method of manufacturing active material |
| JP5341470B2 (en) * | 2008-10-29 | 2013-11-13 | 旭化成株式会社 | ELECTRODE BODY FOR STORAGE ELEMENT, NON-AQUEOUS LITHIUM TYPE STORAGE ELEMENT AND METHOD FOR PRODUCING ELECTRODE BODY FOR STORAGE ELEMENT |
| US8580432B2 (en) | 2008-12-04 | 2013-11-12 | Nanotek Instruments, Inc. | Nano graphene reinforced nanocomposite particles for lithium battery electrodes |
| US9093693B2 (en) * | 2009-01-13 | 2015-07-28 | Samsung Electronics Co., Ltd. | Process for producing nano graphene reinforced composite particles for lithium battery electrodes |
| EP2228854B1 (en) | 2009-03-12 | 2014-03-05 | Belenos Clean Power Holding AG | Nitride and carbide anode materials |
| EP2237346B1 (en) | 2009-04-01 | 2017-08-09 | The Swatch Group Research and Development Ltd. | Electrically conductive nanocomposite material comprising sacrificial nanoparticles and open porous nanocomposites produced thereof |
| US20140370380A9 (en) | 2009-05-07 | 2014-12-18 | Yi Cui | Core-shell high capacity nanowires for battery electrodes |
| US20100291438A1 (en) * | 2009-05-15 | 2010-11-18 | PDC Energy, LLC | Electrode material, lithium-ion battery and method thereof |
| EP2287946A1 (en) | 2009-07-22 | 2011-02-23 | Belenos Clean Power Holding AG | New electrode materials, in particular for rechargeable lithium ion batteries |
| JP2011048992A (en) | 2009-08-26 | 2011-03-10 | Sekisui Chem Co Ltd | Carbon material, electrode material, and lithium ion secondary battery negative electrode material |
| KR101736462B1 (en) | 2009-09-21 | 2017-05-16 | 한화테크윈 주식회사 | Method for manufacturing graphene |
| JP5594656B2 (en) | 2009-09-30 | 2014-09-24 | 国立大学法人名古屋大学 | Method for producing positive electrode material of lithium ion secondary battery |
| WO2011057074A2 (en) | 2009-11-06 | 2011-05-12 | Northwestern University | Electrode material comprising graphene-composite materials in a graphite network |
| US9431649B2 (en) | 2009-11-23 | 2016-08-30 | Uchicago Argonne, Llc | Coated electroactive materials |
| US8975326B2 (en) * | 2010-03-15 | 2015-03-10 | Lei Zhai | Carbon nanotube or graphene-based aerogels |
| CN103053055B (en) | 2010-08-19 | 2016-10-12 | 株式会社半导体能源研究所 | Electrical equipment |
| US20120088151A1 (en) | 2010-10-08 | 2012-04-12 | Semiconductor Energy Laboratory Co., Ltd. | Positive-electrode active material and power storage device |
| US8859143B2 (en) * | 2011-01-03 | 2014-10-14 | Nanotek Instruments, Inc. | Partially and fully surface-enabled metal ion-exchanging energy storage devices |
| KR101093140B1 (en) | 2011-05-25 | 2011-12-13 | 한국과학기술연구원 | Method for preparing reduced graphene oxide and reduced graphene oxide-polymer composite |
| US9218916B2 (en) | 2011-06-24 | 2015-12-22 | Semiconductor Energy Laboratory Co., Ltd. | Graphene, power storage device, and electric device |
| US20120328956A1 (en) | 2011-06-24 | 2012-12-27 | Semiconductor Energy Laboratory Co., Ltd. | Multilayer graphene and power storage device |
| KR20130007429A (en) | 2011-06-24 | 2013-01-18 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Graphene, power storage device, and electric appliance |
| KR101365304B1 (en) * | 2011-10-07 | 2014-02-27 | 주식회사 케이씨씨 | Composite Binder containing graphene and lithium secondary battery comprising the same |
| EP2795701B1 (en) | 2011-12-19 | 2016-11-02 | Solvay Specialty Polymers Italy S.p.A. | Electrode-forming composition |
-
2012
- 2012-12-19 JP JP2012276793A patent/JP6009343B2/en active Active
- 2012-12-21 US US13/724,427 patent/US20130164619A1/en not_active Abandoned
- 2012-12-24 KR KR1020120152142A patent/KR102093094B1/en not_active Expired - Fee Related
- 2012-12-25 CN CN201210571579.8A patent/CN103178239B/en not_active Expired - Fee Related
-
2018
- 2018-06-06 US US16/001,467 patent/US10938035B2/en active Active
-
2020
- 2020-03-17 KR KR1020200032494A patent/KR102256796B1/en not_active Expired - Fee Related
-
2021
- 2021-02-18 US US17/178,286 patent/US11962013B2/en active Active
- 2021-05-21 KR KR1020210065234A patent/KR102329917B1/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20050186378A1 (en) * | 2004-02-23 | 2005-08-25 | Bhatt Sanjiv M. | Compositions comprising carbon nanotubes and articles formed therefrom |
| CN101243566A (en) * | 2005-09-06 | 2008-08-13 | Lg化学株式会社 | Composite binder containing carbon nanotube and lithium secondary battery employing the same |
| CN102077392A (en) * | 2009-01-26 | 2011-05-25 | 丰田自动车株式会社 | Positive electrode for lithium secondary battery and use thereof |
| CN101710619A (en) * | 2009-12-14 | 2010-05-19 | 重庆大学 | Electrode plate for lithium ion battery and manufacturing method thereof |
| WO2011079238A1 (en) * | 2009-12-24 | 2011-06-30 | Aruna Zhamu | Conductive graphene polymer binder for electrochemical cell electrodes |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110010848A (en) * | 2014-01-28 | 2019-07-12 | 株式会社Lg化学 | Surface-coated positive electrode active material, method for preparing same, and positive electrode and lithium secondary battery comprising same |
| CN105489898A (en) * | 2015-12-31 | 2016-04-13 | 深圳市贝特瑞新能源材料股份有限公司 | Conductive waterborne binder and preparation method therefor, and lithium ion battery |
| CN105489898B (en) * | 2015-12-31 | 2019-02-05 | 深圳市贝特瑞新能源材料股份有限公司 | Conductive aqueous binders and preparation method thereof, lithium ion battery |
| CN107425199A (en) * | 2016-05-23 | 2017-12-01 | 中南大学 | A kind of conduction leads lithium difunctionalization graphene oxide composite material and preparation method thereof and the application in lithium sulphur or lithium-air battery |
| CN107425199B (en) * | 2016-05-23 | 2019-12-13 | 中南大学 | Conductive lithium-conducting dual-functional graphene oxide material, preparation method thereof and application of conductive lithium-conducting dual-functional graphene oxide material in lithium-sulfur or lithium-air battery |
| CN107768670A (en) * | 2017-10-23 | 2018-03-06 | 东莞理工学院 | Positive electrode material, preparation method and application, positive electrode preparation method |
| CN114864935A (en) * | 2022-04-19 | 2022-08-05 | 中国科学院过程工程研究所 | Method for preparing high-rate lithium battery negative electrode material from natural graphite spherical tailings |
Also Published As
| Publication number | Publication date |
|---|---|
| US20130164619A1 (en) | 2013-06-27 |
| JP6009343B2 (en) | 2016-10-19 |
| KR102329917B1 (en) | 2021-11-24 |
| US20210175507A1 (en) | 2021-06-10 |
| CN103178239B (en) | 2018-02-23 |
| US10938035B2 (en) | 2021-03-02 |
| KR102093094B1 (en) | 2020-03-25 |
| US11962013B2 (en) | 2024-04-16 |
| KR102256796B1 (en) | 2021-05-27 |
| JP2013152926A (en) | 2013-08-08 |
| US20180287160A1 (en) | 2018-10-04 |
| KR20210064128A (en) | 2021-06-02 |
| KR20200034682A (en) | 2020-03-31 |
| KR20130079232A (en) | 2013-07-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR102329917B1 (en) | Positive electrode for secondary battery and manufacturing method of positive electrode for secondary battery | |
| KR102460865B1 (en) | Method for forming positive electrode for lithium-ion secondary battery | |
| TWI792027B (en) | Lithium secondary battery | |
| CN103258991A (en) | Method for forming negative electrode and method for manufacturing lithium secondary battery | |
| KR20150034643A (en) | Power storage device | |
| CN103633294A (en) | Positive electrode for secondary battery, secondary battery, and method for fabricating positive electrode for secondary battery | |
| CN103715400A (en) | Material for electrode of power storage device, power storage device, and electrical appliance | |
| CN103682360A (en) | Electrode material for power storage device, electrode for power storage device, and power storage device | |
| CN103515603A (en) | Secondary battery | |
| CN104078651A (en) | Method for manufacturing electrode for storage battery | |
| CN103456919A (en) | Negative electrode for power storage device and power storage device | |
| CN104781954A (en) | Electrode for power storage device, power storage device, and manufacturing method of electrode for power storage device | |
| CN105322173B (en) | Method for manufacturing electrode, storage battery, and electronic device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20180223 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |